US6297394B1 - Iron-based catalyst for hydrogenating alpha-, omega-dinitriles - Google Patents
Iron-based catalyst for hydrogenating alpha-, omega-dinitriles Download PDFInfo
- Publication number
- US6297394B1 US6297394B1 US09/622,773 US62277300A US6297394B1 US 6297394 B1 US6297394 B1 US 6297394B1 US 62277300 A US62277300 A US 62277300A US 6297394 B1 US6297394 B1 US 6297394B1
- Authority
- US
- United States
- Prior art keywords
- omega
- alpha
- catalyst
- dinitrile
- range
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
- C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles
Definitions
- the present invention relates to a material useful as catalyst, comprising
- the present invention further relates to processes for hydrogenation of aliphatic alpha, omega-dinitriles in the presence of such materials as catalyst and to the use of such materials as catalyst in the hydrogenation of aliphatic alpha, omega-dinitriles.
- Important requirements for good iron catalysts include high mechanical strength, a long time on stream, a high space-time yield of the products of value, alpha, omega-aminonitrile and/or alpha, omega-diamine, coupled with complete alpha, omega-dinitrile conversion and a very low level of unwanted by-products.
- the hydrogenation of adiponitrile to hexamethylenediamine by-produces varying quantities of, inter alia, tetrahydroazepine (THA), 1-amino-2-cyanocyclopentene (ICCP), 2-aminomethylcyclopentylamine (AMCPA), 1,2-diaminocyclohexane (DCH) and bishexamethylenetriamine (BHMTA).
- TAA tetrahydroazepine
- ICCP 1-amino-2-cyanocyclopentene
- AMCPA 2-aminomethylcyclopentylamine
- DCH 1,2-diaminocyclohexane
- BHMTA bishexamethylenetriamine
- DE-A-2 429 293 discloses in Example 1 that the hydrogenation of adiponitrile in the presence of five times the weight of ammonia at from 93 to 98° C. (inlet temperature into the reactor) or at from 94 to 104° C. (outlet temperature) over an iron catalyst prepared from magnetite by reduction with hydrogen and doped with aluminum oxide, silicon dioxide, calcium oxide and vanadium pentoxide yields 98.22% of hexamethylenediamine comprising 1900 ppm of 1,2-diaminocyclohexane, and in Example 2 that the hydrogenation of adiponitrile in the presence of five times the weight of ammonia at from 93 to 98° C.
- inlet temperature into the reactor or at from 94 to 104° C. (outlet temperature) over an iron catalyst prepared from Labrador hematite ore (Fe 2 O 3 ) by reduction with hydrogen and doped with aluminum oxide, silicon dioxide and calcium oxide yields 98.05% of hexamethylenediamine comprising 3500 ppm of 1,2-diaminocyclohexane.
- an iron catalyst prepared from Labrador hematite ore (Fe 2 O 3 ) by reduction with hydrogen and doped with aluminum oxide, silicon dioxide and calcium oxide yields 98.05% of hexamethylenediamine comprising 3500 ppm of 1,2-diaminocyclohexane.
- the materials of the invention preferably have a BET surface area of from 3 to 20 m 2 /g, a total pore volume of from 0.05 to 0.2 mL/g, an average pore diameter of from 0.03 to 0.1 ⁇ m and a 0.01 to 0.1 ⁇ m pore volume fraction within the range from 50 to 70%.
- weight %ages in (b) and (d) are based on the elements and the weight %ages in (c) are based on the oxides of the alkali and alkaline earth metals. These percentages are based on component (a).
- component (a) comprises from 90 to 100% by weight, preferably from 92 to 99% by weight, based on (a), of iron oxides, iron hydroxides, iron oxyhydroxides or mixtures thereof.
- iron oxides iron hydroxides, iron oxyhydroxides or mixtures thereof.
- the atomic ratio of oxygen to iron is preferably within the range from 1.25:1 to 1.45:1, preferably within the range from 1.3:1 to 1.4:1, particularly preferably equal to 1.33:1, i.e., pure magnetite.
- magnetite is synthesized, it is possible to start from very pure metallic iron or from very pure iron (II) compounds and/or iron (III) compounds, to which the doping elements are added subsequently in the form of suitable compounds.
- component (b) comprises from 0.001 to 0.3% by weight, preferably from 0.01 to 0.2% by weight, especially from 0.01 to 0.1% by weight, of a promoter based on 2, 3, 4 or 5, preferably 3, 4 or 5, elements selected from the group consisting of aluminum, zirconium, silicon, titanium and vanadium, especially the combination of aluminum, silicon and titanium.
- component (c) comprises from 0 to 0.3% by weight, preferably from 0.01 to 0.2% by weight, particularly preferably from 0.01 to 0.1% by weight, of a compound based on an alkali or alkaline earth metal selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, magnesium and calcium, preferably calcium and/or magnesium.
- the materials of the invention comprise from 0.001 to 1% by weight, preferably from 0.001 to 0.3% by weight, especially from 0.01 to 0.2% by weight, of manganese.
- the catalysts of the invention can be supported or unsupported catalysts.
- support materials are porous oxides such as aluminum oxide, silicon dioxide, alumosilicates, lanthanum oxide, titanium dioxide, zirconium dioxide, magnesium oxide, zinc oxide, and zeolites and also activated carbon or mixtures thereof.
- Preparation is generally effected by precipitating one or more precursors of component (a) if desired together with precursors of promoter components (b), (d) and if desired with precursors of components (c) in the presence or absence of support materials (depending on which catalyst type is desired), if desired processing the resulting catalyst precursor into extrudates or tablets, drying and then calcining.
- Supported catalysts are generally also obtainable by saturating the support with a solution of components (a), (b), (d) and if desired (c), it being possible to add the individual components simultaneously or in succession, or by spraying the components (a), (b), (d) and if desired (c) onto the support in a conventional manner.
- Suitable precursors for components (a) are generally readily water-soluble salts of iron such as nitrates, chlorides, acetates, formates and sulfates, preferably nitrates.
- Suitable precusors for components (b) and (d) are generally readily water-soluble salts or complexes of the aforementioned metals and semimetals such as nitrates, chlorides, acetates, formates and sulfates, preferably nitrates.
- Suitable precursors for components (c) are generally readily water-soluble salts of the aforementioned alkali metals and alkaline earth metals such as hydroxides, carbonates, nitrates, chlorides, acetates, formates and sulfates, preferably hydroxides and carbonates.
- Precipitation is generally effected from aqueous solutions, selectively by adding precipitating reagents, by changing the pH or by changing the temperature.
- the catalyst prematerial thus obtained is customarily dried at a temperature generally within the range from 80 to 150° C., preferably within the range from 80 to 120° C.
- Calcining is customarily effected at a temperature within the range from 150 to 500° C., preferably within the range from 200 to 450° C., in a gas stream of air or nitrogen.
- the catalyst material obtained is generally exposed to a reducing atmosphere (“activation”), for example by exposing it at a temperature within the range from 200 to 500° C., preferably within the range from 250 to 400° C., to a hydrogen atmosphere or a gas mixture comprising hydrogen and an inert gas such as nitrogen for a period within the range from 2 to 24 hours.
- activation for example by exposing it at a temperature within the range from 200 to 500° C., preferably within the range from 250 to 400° C., to a hydrogen atmosphere or a gas mixture comprising hydrogen and an inert gas such as nitrogen for a period within the range from 2 to 24 hours.
- activation reducing atmosphere
- the volume hourly space velocity for this is preferably 200 L per liter of catalyst per hour.
- the activation of the catalyst is carried out directly in the synthesis reactor, since this customarily obviates an otherwise necessary intermediary step, namely the passivation of the surface by means of oxygen-nitrogen mixtures such as air at a temperature which is customarily within the range from 20 to 80° C., preferably within the range from 25 to 35° C.
- the activation of passivated catalysts is then preferably carried out in the synthesis reactor in a hydrogen-comprising atmosphere at a temperature within the range from 180 to 500° C., preferably within the range from 200 to 350° C.
- the catalysts can be used as fixed bed catalysts in upflow or trickle mode or as suspension catalysts.
- the starting materials used in the process of the present invention are aliphatic alpha, omega-dinitriles of the general formula I
- n is an integer from 1 to 10, especially 2, 3, 4, 5 or 6.
- Particularly preferred compounds I are succinonitrile, glutaronitrile, adiponitrile, pimelonitrile and suberonitrile, most preferably adiponitrile.
- alpha, omega-dinitriles obtained by hydrocyanation in the presence of phosphorus catalysts of an alpha, omega-diene having two carbon atoms fewer, such as adiponitrile by addition of hydrocyanic acid to butadiene or 3-pentenenitrile in the presence of nickel(0) compounds and triaryl phosphites.
- Such alpha, omega-dinitriles may comprise traces of phosphorus compounds, from about 1 to 50 ppm, reckoned as phoshorus and based on alpha, omega-dinitrile. Removing these phosphorus compounds in whole or in part to obtain weight fractions of phosphorus compound of less than 5 ppm, preferably less than 1 ppm, makes it possible to raise the long catalyst times on stream obtained in the process of the invention and in the use of the invention even further.
- the distillation can advantageously be carried out at a pressure of from 1 to 100 mbar, preferably of from 10 to 200 mbar, in which case the adiponitrile is usually obtained as overhead product, since the phosphorus compounds are essentially less volatile than adiponitrile.
- the process of the present invention can hydrogenate the above-described dinitriles I by means of a catalyst, preferably in the presence of a solvent, to alpha, omega-aminonitriles of the general formula II
- n is as defined above.
- Particularly preferred aminonitriles II are those in which n is 2, 3, 4, 5 or 6, especially 4, i.e., 4-aminobutanenitrile, 1,5-aminopentanenitrile, 1,6-aminohexanenitrile (“6-aminocapronitrile”), 1,7-aminoheptanenitrile and 1,8-aminooctanenitrile, most preferably 6-aminocapronitrile.
- the temperature will be customarily selected from within the range from 40 to 150° C., preferably from within the-range from 50 to 100° C., particularly preferably from within the range from 60 to 90° C.
- the pressure is generally chosen from within the range from 2 to 30 Mpa, preferably from within the range from 3 to 30 Mpa, particularly preferably from within the range from 4 to 9 Mpa.
- the residence time is essentially dependent on the desired yield, selectivity and if conversion is complete; the residence time may customarily be chosen so as to obtain maximum yield at complete conversion, for example from within the range from 50 to 275 min, preferably from within the range from 70 to 200 min.
- the suspension process solvent is preferably selected from ammonia, amines, diamines and triamines having from 1 to 6 carbon atoms such as trimethylamine, triethylamine, tripropylamine and tributylamine or alcohols, especially methanol and ethanol, and is particularly preferably ammonia.
- the dinitrile concentration is advantageously chosen from within the range from 10 to 90% by weight, preferably from within the range from 30 to 80% by weight, particularly preferably from within the range from 40 to 70% by weight, based on the sum total of dinitrile and solvent.
- the amount of catalyst is generally chosen so that the catalyst quantity is within the range from 1 to 50% by weight, preferably within the range from 5 to 20% by weight, based on the amount of dinitrile used.
- the suspension hydrogenation can be carried out batchwise or, preferably, continuously, generally in the liquid phase.
- the hydrogenation can also be carried out batchwise or continuously in a fixed bed reactor in trickle or upflow mode with a straight pass or with product recycling, in which case it is customary to select a temperature from within the range from 20 to 150° C., preferably from within the range from 30 to 90° C., and a pressure generally from within the range of from 2 to 40 Mpa, preferably from within the range from 3 to 30 Mpa.
- the hydrogenation is preferably carried out in the presence of a solvent, preferably ammonia, amines, diamines and triamines, having from 1 to 6 carbon atoms, such as trimethylamine, triethylamine, tripropylamine and tributylamine, or alcohol, preferably methanol and ethanol, particularly preferably ammonia.
- a solvent preferably ammonia, amines, diamines and triamines, having from 1 to 6 carbon atoms, such as trimethylamine, triethylamine, tripropylamine and tributylamine, or alcohol, preferably methanol and ethanol, particularly preferably ammonia.
- the ammonia content is within the range from 1 to 10 g, preferably within the range from 2 to 6 g, per gram of adiponitrile.
- a catalyst space velocity which is within the range from 0.1 to 2.0 kg, preferably within the range from 0.3 to 1.0 kg, of adiponitrile/L x h.
- the hydrogenation can be carried out in a customary hydrogenation reactor.
- the ratio of aminonitriles (II) to diamines (III) can be controlled through specific choice of temperature and catalyst space velocity.
- adiponitrile as alpha, omega-dinitrile affords a mixture which, as well as the solvent, very predominantly comprises 6-aminocapronitrile, hexamethylenediamine and unconverted adiponitrile, which may include especially hexamethyleneimine, 2-aminomethylcyclopentylamine, 1,2-diaminocyclohexane, tetrahydroazepine and bishexanemethylenetriamine as impurities.
- 6-aminocapronitrile, hexamethylenediamine and an essentially adiponitrile portion from the mixture can be effected in a conventional manner, preferably by distillation, for example as described in DE-A-19 500 222 or German Application 19 548 289.1, simultaneously or in succession.
- the process of the invention can hydrogenate the above-described dinitriles I by means of a catalyst, preferably in the presence of a solvent, to alpha, omega-diamines of the general formula III
- n is as defined above.
- diamines III are those in which n is 2, 3, 4, 5 or 6, especially 4, i.e., 4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane (“hexamethylenediamine”), 1,7-diaminoheptane and 1,8-diaminooctane, most preferably 1,6-diaminohexane.
- the temperature will be customarily selected from within the range from 60 to 200° C., preferably from within the range from 60 to 180° C., particularly preferably from within the range from 70 to 130° C.
- the pressure is generally chosen from within the range from 2 to 30 Mpa, preferably from within the range from 3 to 30 Mpa, particularly preferably from within the range from 4 to 20 Mpa.
- the residence time is essentially dependent on the desired yield and selectivity if conversion is complete; the residence time may customarily be chosen so as to obtain maximum yield at complete conversion, for example from within the range from 50 to 300 min, preferably from within the range from 70 to 200 min.
- the suspension process solvent is preferably selected from ammonia, amines, diamines and triamines having from 1 to 6 carbon atoms such as trimethylamine, triethylamine, tripropylamine and tributylamine or alcohols, especially methanol and ethanol, and is particularly preferably ammonia.
- the dinitrile concentration is advantageously chosen from within the range from 10 to 90% by weight, preferably from within the range from 30 to 80% by weight, particularly preferably from within the range from 40 to 70% by weight, based on the sum total of dinitrile and solvent.
- the amount of catalyst is generally chosen so that the catalyst quantity is within the range from 1 to 50% by weight, preferably within the range from 5 to 20% by weight, based on the amount of dinitrile used.
- the suspension hydrogenation can be carried out batchwise or, preferably, continuously, generally in the liquid phase.
- the hydrogenation can also be carried out batchwise or continuously in a fixed bed reactor in trickle or upflow mode with a straight pass or with product recycling, in which case it is customary to select a temperature from within the range from 70 to 200° C., preferably from within the range from 80 to 150° C., and a pressure generally from within the range of from 2 to 40 Mpa, preferably from within the range from 3 to 30 Mpa.
- the hydrogenation is preferably carried out in the presence of a solvent, preferably ammonia, amines, diamines and triamines, having from 1 to 6 carbon atoms, such as trimethylamine, triethylamine, tripropylamine and tributylamine, or alcohol, preferably methanol and ethanol, particularly preferably ammonia.
- a solvent preferably ammonia, amines, diamines and triamines, having from 1 to 6 carbon atoms, such as trimethylamine, triethylamine, tripropylamine and tributylamine, or alcohol, preferably methanol and ethanol, particularly preferably ammonia.
- the ammonia content is within the range from 1 to 10 g, preferably within the range from 2 to 6 g, per gram of adiponitrile.
- a catalyst space velocity which is within the range from 0.1 to 2.0 kg, preferably within the range from 0.3 to 1.5 kg, of adiponitrile/L x h.
- the hydrogenation can be carried out in a customary hydrogenation reactor.
- adiponitrile as alpha, omega-dinitrile affords a mixture which, as well as the solvent, very predominantly comprises hexamethylenediamine, which may include especially 6-aminocapronitrile, hexamethyleneimine, 2-aminomethylcyclopentylamine, 1,2-diaminocyclohexane, tetrahydroazepine and bishexanemethylenetriamine as impurities.
- hexamethylenediamine which may include especially 6-aminocapronitrile, hexamethyleneimine, 2-aminomethylcyclopentylamine, 1,2-diaminocyclohexane, tetrahydroazepine and bishexanemethylenetriamine as impurities.
- the purification of the crude hexamethylenediaminfe obtained after removal of the solvent is in general preferably effected by distillation.
- alpha, omega-Aminonitriles and alpha, omega-diamines are important starting compounds for producing nylon-6,6 and/or nylon-6.
- ADN adiponitrile
- ACN 6-aminocapronitrile
- HMD hexamethylenediamine
- DCH 1,2-diaminocyclohexane
- AMCPA 2-aminomethylcyclopentylamine
- BHMTA bishexamethylenetriamine
- ICCP 1-amino-2-cyanocyclopentene
- THA tetrahydroazepine
- HMI hexamethyleneimine
- the catalyst was prepared by heating a magnetite ore under nitrogen at 1500° C. for six hours.
- the magnetite ore used had the following composition: 72% by weight of Fe, 0.06% by weight of Al, 0.03% by weight of Ca, 0.04% by weight of Mg, 0.10% by weight of Si, 0.01% by weight of Ti, 0.13% by weight of Mn, remainder oxygen.
- the cooled melt block was comminuted in a jaw crusher, and a sieve fraction of particle size 1.5-3 mm was separated out by sieving.
- the oxidic catalyst was reduced in an H 2 /N 2 stream at 450° C. for 72 hours. After cooling down to room temperature under nitrogen, the Fe catalyst was passivated with an N 2 /air stream (24 hours with 1% of air in nitrogen), care being taken to ensure that the temperature in the catalyst bed did not rise above 45° C.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/851,214 US6852669B2 (en) | 1998-03-06 | 2001-05-08 | Hydrogenation catalyst |
US10/776,544 US7091153B2 (en) | 1998-03-06 | 2004-02-12 | Hydrogenation catalyst |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19809687 | 1998-03-06 | ||
DE19809687A DE19809687A1 (de) | 1998-03-06 | 1998-03-06 | Hydrierkatalysator |
PCT/EP1999/001150 WO1999044984A1 (de) | 1998-03-06 | 1999-02-23 | Katalysator auf der basis von eisen zur hydrierung von alpha, omega-dinitrilen |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1999/001150 A-371-Of-International WO1999044984A1 (de) | 1998-03-06 | 1999-02-23 | Katalysator auf der basis von eisen zur hydrierung von alpha, omega-dinitrilen |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/851,214 Division US6852669B2 (en) | 1998-03-06 | 2001-05-08 | Hydrogenation catalyst |
Publications (1)
Publication Number | Publication Date |
---|---|
US6297394B1 true US6297394B1 (en) | 2001-10-02 |
Family
ID=7859988
Family Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/622,773 Expired - Lifetime US6297394B1 (en) | 1998-03-06 | 1999-02-23 | Iron-based catalyst for hydrogenating alpha-, omega-dinitriles |
US09/851,214 Expired - Fee Related US6852669B2 (en) | 1998-03-06 | 2001-05-08 | Hydrogenation catalyst |
US10/776,544 Expired - Fee Related US7091153B2 (en) | 1998-03-06 | 2004-02-12 | Hydrogenation catalyst |
Family Applications After (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/851,214 Expired - Fee Related US6852669B2 (en) | 1998-03-06 | 2001-05-08 | Hydrogenation catalyst |
US10/776,544 Expired - Fee Related US7091153B2 (en) | 1998-03-06 | 2004-02-12 | Hydrogenation catalyst |
Country Status (27)
Country | Link |
---|---|
US (3) | US6297394B1 (hu) |
EP (1) | EP1071653B1 (hu) |
JP (1) | JP2002505192A (hu) |
KR (1) | KR100553283B1 (hu) |
CN (1) | CN1185205C (hu) |
AR (1) | AR018146A1 (hu) |
AT (1) | ATE247623T1 (hu) |
AU (1) | AU2835699A (hu) |
BG (1) | BG64753B1 (hu) |
BR (1) | BR9908505A (hu) |
CA (1) | CA2322185C (hu) |
CZ (1) | CZ294316B6 (hu) |
DE (2) | DE19809687A1 (hu) |
EA (1) | EA003285B1 (hu) |
ES (1) | ES2207184T3 (hu) |
HU (1) | HUP0101241A3 (hu) |
ID (1) | ID25619A (hu) |
MY (1) | MY122207A (hu) |
NO (1) | NO317588B1 (hu) |
PL (1) | PL342900A1 (hu) |
PT (1) | PT1071653E (hu) |
SI (1) | SI1071653T1 (hu) |
SK (1) | SK12382000A3 (hu) |
TR (1) | TR200002588T2 (hu) |
TW (1) | TW518252B (hu) |
UA (1) | UA66841C2 (hu) |
WO (1) | WO1999044984A1 (hu) |
Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040254070A1 (en) * | 2001-10-23 | 2004-12-16 | Andreas Ansmann | Iron-containing oxidic material suitable for use as hydrogenation catalyst precursor |
US20040254059A1 (en) * | 2001-10-23 | 2004-12-16 | Andreas Ansmann | Iron-containing material suitable for use as hydrogenation catalyst |
US20060223974A1 (en) * | 2003-05-14 | 2006-10-05 | Basf Aktiengesellschaft | Polyamides |
US20060258889A1 (en) * | 2003-09-10 | 2006-11-16 | Basf Aktiengesellschaft | Method for the production of diaminoxylene by continuous hydrogenation of liquid phthalonitrile |
US20080015267A1 (en) * | 2006-07-14 | 2008-01-17 | Headwaters Nanokinetix, Inc. | Fischer-tropsch catalysts incorporating promoter for increasing yields of c5+ hydrocarbons and methods for making and using same |
US20090069590A1 (en) * | 2006-05-09 | 2009-03-12 | Basf Aktiengesellschaft | Process for preparing aminoalkylnitriles and diamines from such nitriles |
US20100029976A1 (en) * | 2007-03-01 | 2010-02-04 | Basf Se | Method for producing tetraethylenepentamine |
US20100029991A1 (en) * | 2007-03-01 | 2010-02-04 | Basf Se | Method for producing triethylenetetramine |
US20100094057A1 (en) * | 2007-03-01 | 2010-04-15 | Basf Se | Method for producing ethylenediamine |
US20100121064A1 (en) * | 2007-03-01 | 2010-05-13 | Basf Se | Novel method for producing teta by means of eddn |
US7728174B2 (en) | 2005-08-02 | 2010-06-01 | Basf Se | Continuous hydrogenation processes for the preparation of xylylenediamines |
US7960590B2 (en) | 2007-03-01 | 2011-06-14 | Basf Se | Method for producing ethyleneamines from untreated AAN |
US8586795B2 (en) | 2009-06-18 | 2013-11-19 | Basf Se | Methyl-substituted teta compounds |
US20160045901A1 (en) * | 2013-03-19 | 2016-02-18 | Korea Institute Of Energy Research | Iron-based catalyst and method for preparing the same and use thereof |
WO2017142898A1 (en) | 2016-02-16 | 2017-08-24 | Invista North America S.A R.L. | Promoter for selective nitrile hydrogenation |
WO2018050555A1 (de) | 2016-09-19 | 2018-03-22 | Basf Se | Verfahren zur herstellung von polyaminen ausgehend von dinitrilen und/oder aminonitrilen |
US11806699B2 (en) | 2008-12-08 | 2023-11-07 | Sasol Technology (Pty.) Limited | Olefin selective FT catalyst composition and preparation thereof |
Families Citing this family (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU2006278461A1 (en) | 2005-08-03 | 2007-02-15 | Ccmi Corporation | Enhancement of surface-active solid-phase heterogeneous catalysts |
JP4670603B2 (ja) * | 2005-11-18 | 2011-04-13 | 株式会社デンソー | 触媒用粒子およびその製造方法 |
US8031804B2 (en) * | 2006-04-24 | 2011-10-04 | Parkervision, Inc. | Systems and methods of RF tower transmission, modulation, and amplification, including embodiments for compensating for waveform distortion |
EP1900428B1 (en) | 2006-08-09 | 2016-01-06 | Mitsubishi Gas Chemical Company, Inc. | Production method of primary amines and catalysts for producing primary amines |
US8142748B2 (en) * | 2007-09-17 | 2012-03-27 | Shell Oil Company | Catalyst composition useful in the catalytic reduction of sulfur compound contained in a gas stream and a method of making and using such composition |
EP2193841A1 (en) * | 2008-12-08 | 2010-06-09 | Sasol Technology (Proprietary) Limited | Hydrocarbon synthesis catalyst and process with improved selectivity to short chain products |
CN103764617B (zh) | 2011-08-31 | 2015-12-02 | 巴斯夫欧洲公司 | 通过使edfa和/或edmfa与hcn反应制备eddn和/或edmn的方法 |
WO2013030249A1 (de) | 2011-08-31 | 2013-03-07 | Basf Se | Verfahren zur herstellung von aminen durch hydrierung von nitrilen |
WO2013030144A1 (de) | 2011-08-31 | 2013-03-07 | Basf Se | Verfahren zur herstellung von eddn, edmn, teta und deta |
WO2013030255A1 (de) | 2011-08-31 | 2013-03-07 | Basf Se | Verfahren zur herstellung von eddn und/oder edmn sowie verfahren zur herstellung von deta und/oder teta |
WO2013030023A1 (de) | 2011-08-31 | 2013-03-07 | Basf Se | Verfahren zur herstellung von eddn und/oder edmn sowie ein verfahren zur herstellung von deta und/oder teta |
US9012638B2 (en) | 2011-08-31 | 2015-04-21 | Basf Se | Process for preparing EDDN and/or EDMN by conversion of FACH and EDA |
US8946459B2 (en) | 2011-08-31 | 2015-02-03 | Basf Se | Process for preparing EDDN and/or EDMN by reacting EDFA and/or EDMFA with HCN |
WO2013030254A1 (de) | 2011-08-31 | 2013-03-07 | Basf Se | Verfahren zur herstellung von teta und/oder deta |
IN2014CN00791A (hu) | 2011-08-31 | 2015-04-03 | Basf Se | |
CN103764614A (zh) | 2011-08-31 | 2014-04-30 | 巴斯夫欧洲公司 | Eddn或edmn氢化反应出料的后处理方法 |
US9096497B2 (en) | 2011-08-31 | 2015-08-04 | Basf Se | Process for preparing EDDN and EDMN |
US8952156B2 (en) | 2011-08-31 | 2015-02-10 | Basf Se | Process for working up reaction outputs from the hydrogenation of EDDN or EDMN |
EP2751068A1 (de) | 2011-08-31 | 2014-07-09 | Basf Se | Verfahren zur herstellung von eddn und/oder edmn durch umsetzung von fach und eda |
WO2013030259A1 (de) | 2011-08-31 | 2013-03-07 | Basf Se | Verfahren zur herstellung von teta |
WO2013030174A1 (de) | 2011-08-31 | 2013-03-07 | Basf Se | Verfahren zur herstellung von edfa und/oder edmfa und deta und/oder teta |
CN105073712B (zh) | 2013-01-30 | 2017-09-22 | 巴斯夫欧洲公司 | 2,6‑双(氨基甲基)哌啶衍生物 |
CN105051003B (zh) | 2013-02-28 | 2017-05-03 | 巴斯夫欧洲公司 | 使用不含so2的氢氰酸制备eda的方法 |
WO2014131674A2 (en) | 2013-03-01 | 2014-09-04 | Basf Se | Amine composition |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3696153A (en) | 1969-07-11 | 1972-10-03 | Du Pont | Hydrogenation of adiponitrile |
DE2429293A1 (de) | 1973-09-12 | 1975-03-20 | Ici Ltd | Katalysatoren und ihre verwendung zur hydrierung |
US3986985A (en) | 1973-09-12 | 1976-10-19 | Imperial Chemical Industries Limited | Catalysts for hydrogenation |
US4064172A (en) | 1973-09-12 | 1977-12-20 | Imperial Chemical Industries Limited | Hexamethylene diamine by hydrogenation of adiponitrile in presence of an activated iron oxide catalyst |
US4282381A (en) | 1980-08-21 | 1981-08-04 | E. I. Du Pont De Nemours And Company | Process for purifying hexamethylenediamine |
US5527946A (en) | 1994-12-27 | 1996-06-18 | Basf Aktiengesellschaft | Preparation of aliphatic alpha, omega-aminonitriles |
WO1998011059A1 (de) | 1996-09-10 | 1998-03-19 | Basf Aktiengesellschaft | Verfahren zur herstellung von aliphatischen alpha, omega-aminonitrilen |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE848654C (de) | 1950-08-19 | 1952-09-08 | Basf Ag | Verfahren zur Herstellung von partiellen Hydrierungsprodukten des Adipinsaeuredinitrils |
BE758035A (fr) * | 1969-10-29 | 1971-04-26 | Halcon International Inc | Procede de couplage par reduction de composes organiques halogenes |
JPH0820666B2 (ja) * | 1987-02-24 | 1996-03-04 | 旭光学工業株式会社 | フアインダ−装置 |
DE19533484A1 (de) * | 1995-09-12 | 1997-03-13 | Basf Ag | Monomodale und polymodale Katalysatorträger und Katalysatoren mit engen Porengrößenverteilungen und deren Herstellverfahren |
DE10151559A1 (de) * | 2001-10-23 | 2003-04-30 | Basf Ag | Als Katalysator geeignete Masse |
-
1998
- 1998-03-06 DE DE19809687A patent/DE19809687A1/de not_active Withdrawn
-
1999
- 1999-02-23 TR TR2000/02588T patent/TR200002588T2/xx unknown
- 1999-02-23 BR BR9908505-4A patent/BR9908505A/pt not_active Application Discontinuation
- 1999-02-23 CN CNB998037192A patent/CN1185205C/zh not_active Ceased
- 1999-02-23 EP EP99908940A patent/EP1071653B1/de not_active Expired - Lifetime
- 1999-02-23 SK SK1238-2000A patent/SK12382000A3/sk unknown
- 1999-02-23 WO PCT/EP1999/001150 patent/WO1999044984A1/de active IP Right Grant
- 1999-02-23 AU AU28356/99A patent/AU2835699A/en not_active Abandoned
- 1999-02-23 HU HU0101241A patent/HUP0101241A3/hu unknown
- 1999-02-23 DE DE59906684T patent/DE59906684D1/de not_active Expired - Lifetime
- 1999-02-23 PT PT99908940T patent/PT1071653E/pt unknown
- 1999-02-23 UA UA2000105672A patent/UA66841C2/uk unknown
- 1999-02-23 CZ CZ20003237A patent/CZ294316B6/cs not_active IP Right Cessation
- 1999-02-23 PL PL99342900A patent/PL342900A1/xx unknown
- 1999-02-23 EA EA200000894A patent/EA003285B1/ru not_active IP Right Cessation
- 1999-02-23 ID IDW20001721A patent/ID25619A/id unknown
- 1999-02-23 US US09/622,773 patent/US6297394B1/en not_active Expired - Lifetime
- 1999-02-23 KR KR1020007009834A patent/KR100553283B1/ko not_active IP Right Cessation
- 1999-02-23 JP JP2000534529A patent/JP2002505192A/ja not_active Withdrawn
- 1999-02-23 SI SI9930440T patent/SI1071653T1/xx unknown
- 1999-02-23 AT AT99908940T patent/ATE247623T1/de not_active IP Right Cessation
- 1999-02-23 CA CA002322185A patent/CA2322185C/en not_active Expired - Fee Related
- 1999-02-23 ES ES99908940T patent/ES2207184T3/es not_active Expired - Lifetime
- 1999-03-05 AR ARP990100943A patent/AR018146A1/es unknown
- 1999-03-05 MY MYPI99000815A patent/MY122207A/en unknown
- 1999-03-05 TW TW088103356A patent/TW518252B/zh not_active IP Right Cessation
-
2000
- 2000-09-05 NO NO20004424A patent/NO317588B1/no unknown
- 2000-09-18 BG BG104773A patent/BG64753B1/bg unknown
-
2001
- 2001-05-08 US US09/851,214 patent/US6852669B2/en not_active Expired - Fee Related
-
2004
- 2004-02-12 US US10/776,544 patent/US7091153B2/en not_active Expired - Fee Related
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3696153A (en) | 1969-07-11 | 1972-10-03 | Du Pont | Hydrogenation of adiponitrile |
DE2429293A1 (de) | 1973-09-12 | 1975-03-20 | Ici Ltd | Katalysatoren und ihre verwendung zur hydrierung |
US3986985A (en) | 1973-09-12 | 1976-10-19 | Imperial Chemical Industries Limited | Catalysts for hydrogenation |
US4064172A (en) | 1973-09-12 | 1977-12-20 | Imperial Chemical Industries Limited | Hexamethylene diamine by hydrogenation of adiponitrile in presence of an activated iron oxide catalyst |
US4282381A (en) | 1980-08-21 | 1981-08-04 | E. I. Du Pont De Nemours And Company | Process for purifying hexamethylenediamine |
US5527946A (en) | 1994-12-27 | 1996-06-18 | Basf Aktiengesellschaft | Preparation of aliphatic alpha, omega-aminonitriles |
WO1996020166A1 (de) | 1994-12-27 | 1996-07-04 | Basf Aktiengesellschaft | Verfahren zur herstellung von aliphatischen alpha,omega-aminonitrilen |
WO1998011059A1 (de) | 1996-09-10 | 1998-03-19 | Basf Aktiengesellschaft | Verfahren zur herstellung von aliphatischen alpha, omega-aminonitrilen |
Non-Patent Citations (2)
Title |
---|
Ind.Org.Chem.3, 1988,266. |
Weissermel/Arpe, INdustrielle Organische Chemie, Verlag Chemie, 3rd Edition, (1988) p. 266. |
Cited By (29)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040254059A1 (en) * | 2001-10-23 | 2004-12-16 | Andreas Ansmann | Iron-containing material suitable for use as hydrogenation catalyst |
US7115781B2 (en) | 2001-10-23 | 2006-10-03 | Basf Aktiengesellschaft | Iron-containing oxidic material suitable for use as hydrogenation catalyst precursor |
US7875740B2 (en) * | 2001-10-23 | 2011-01-25 | Basf Aktiengesellschaft | Iron-containing material suitable for use as hydrogenation catalyst |
US20040254070A1 (en) * | 2001-10-23 | 2004-12-16 | Andreas Ansmann | Iron-containing oxidic material suitable for use as hydrogenation catalyst precursor |
US7666976B2 (en) * | 2003-05-14 | 2010-02-23 | Basf Aktiengesellschaft | Polyamides |
US20060223974A1 (en) * | 2003-05-14 | 2006-10-05 | Basf Aktiengesellschaft | Polyamides |
US20060258889A1 (en) * | 2003-09-10 | 2006-11-16 | Basf Aktiengesellschaft | Method for the production of diaminoxylene by continuous hydrogenation of liquid phthalonitrile |
US7339080B2 (en) | 2003-09-10 | 2008-03-04 | Basf Aktiengesellschaft | Method for the production of diaminoxylene by continuous hydrogenation of liquid phthalonitrile |
US7728174B2 (en) | 2005-08-02 | 2010-06-01 | Basf Se | Continuous hydrogenation processes for the preparation of xylylenediamines |
US20090069590A1 (en) * | 2006-05-09 | 2009-03-12 | Basf Aktiengesellschaft | Process for preparing aminoalkylnitriles and diamines from such nitriles |
US8497399B2 (en) | 2006-05-09 | 2013-07-30 | Basf Se | Process for preparing aminoalkyl nitriles and diamines from such nitriles |
US8063239B2 (en) | 2006-05-09 | 2011-11-22 | Basf Se | Process for preparing aminoalkylnitriles and diamines from such nitriles |
US20080015267A1 (en) * | 2006-07-14 | 2008-01-17 | Headwaters Nanokinetix, Inc. | Fischer-tropsch catalysts incorporating promoter for increasing yields of c5+ hydrocarbons and methods for making and using same |
US7709541B2 (en) * | 2006-07-14 | 2010-05-04 | Headwaters Technology Innovation, Llc | Fischer-Tropsch catalysts incorporating promoter for increasing yields of C5+ hydrocarbons and methods for making and using same |
US20100029976A1 (en) * | 2007-03-01 | 2010-02-04 | Basf Se | Method for producing tetraethylenepentamine |
US8440852B2 (en) | 2007-03-01 | 2013-05-14 | Basf Se | Method for producing tetraethylenepentamine |
US7915454B2 (en) | 2007-03-01 | 2011-03-29 | Basf Se | Method for producing ethylenediamine |
US7960591B2 (en) | 2007-03-01 | 2011-06-14 | Basf Se | Method for producing triethylenetetramine |
US7960590B2 (en) | 2007-03-01 | 2011-06-14 | Basf Se | Method for producing ethyleneamines from untreated AAN |
US20100121064A1 (en) * | 2007-03-01 | 2010-05-13 | Basf Se | Novel method for producing teta by means of eddn |
US8299249B2 (en) | 2007-03-01 | 2012-10-30 | Basf Se | Method for producing TETA by means of EDDN |
US20100029991A1 (en) * | 2007-03-01 | 2010-02-04 | Basf Se | Method for producing triethylenetetramine |
US20100094057A1 (en) * | 2007-03-01 | 2010-04-15 | Basf Se | Method for producing ethylenediamine |
US11806699B2 (en) | 2008-12-08 | 2023-11-07 | Sasol Technology (Pty.) Limited | Olefin selective FT catalyst composition and preparation thereof |
US8586795B2 (en) | 2009-06-18 | 2013-11-19 | Basf Se | Methyl-substituted teta compounds |
US20160045901A1 (en) * | 2013-03-19 | 2016-02-18 | Korea Institute Of Energy Research | Iron-based catalyst and method for preparing the same and use thereof |
US9776175B2 (en) * | 2013-03-19 | 2017-10-03 | Korea Institute Of Energy Research | Iron-based catalyst and method for preparing the same and use thereof |
WO2017142898A1 (en) | 2016-02-16 | 2017-08-24 | Invista North America S.A R.L. | Promoter for selective nitrile hydrogenation |
WO2018050555A1 (de) | 2016-09-19 | 2018-03-22 | Basf Se | Verfahren zur herstellung von polyaminen ausgehend von dinitrilen und/oder aminonitrilen |
Also Published As
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6297394B1 (en) | Iron-based catalyst for hydrogenating alpha-, omega-dinitriles | |
CA2342177C (en) | Improved method for simultaneous preparation of 6-aminocapronitrile and hexamethylene diamine | |
US6265602B1 (en) | Method for hydrogenating aliphatic alpha-, omega-dinitriles | |
KR20000035988A (ko) | 6-아미노카프로니트릴 및 헥사메틸렌디아민의 병산 방법 | |
US6222059B1 (en) | Process for the manufacture of aliphatic alpha, omega amino nitriles | |
US6278023B1 (en) | Method for producing aliphatic alpha-, omega-diamines | |
US6255521B1 (en) | Method for producing aliphatic alpha, omega-amino nitriles | |
US7875740B2 (en) | Iron-containing material suitable for use as hydrogenation catalyst | |
US20040254070A1 (en) | Iron-containing oxidic material suitable for use as hydrogenation catalyst precursor | |
MXPA00008228A (en) | Iron-based catalyst for hydrogenating alpha-, omega-dinitriles | |
MXPA00008159A (en) | Method for producing aliphatic alpha-, omega-diamines | |
MXPA00001787A (en) | Method for producing aliphatic alpha, omega-amino nitriles |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: BASF AKTIENGESELLSCHAFT, GERMANY Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:VOIT, GUIDO;FISCHER, ROLF;BASSLER, PETER;AND OTHERS;REEL/FRAME:011101/0232 Effective date: 19990318 |
|
STCF | Information on status: patent grant |
Free format text: PATENTED CASE |
|
FPAY | Fee payment |
Year of fee payment: 4 |
|
FPAY | Fee payment |
Year of fee payment: 8 |
|
FPAY | Fee payment |
Year of fee payment: 12 |